PhD RESEARCH PROPOSAL

Applicant

I, Evariste UWAMAHORO from Rwanda, I got a bachelor’s degree in

Chemistry from the University of Rwanda in 2015 and in 2017 pursue a

master’s degree in Materials science at Zhejiang Sci-Tech University.

Achievements during Master’s study

Academic papers
[1].Uwamahoro Evariste, Guohua Jiang, Bo Yu, Yongkun Liu, Pianpian Ma. Electrodeposition
of manganese-nickel-cobalt sulfides on reduced graphene oxide/nickel foam for high-
performance asymmetric supercapacitors [J]. Journal of Electronic Materials, 2020, 49: 922-
930.
[2].Uwamahoro Evariste, Guohua Jiang, Bo Yu, Yongkun Liu, Zheng Huang, Qiuling
Lu, Pianpian Ma. Hierarchical mesoporous Zn-Ni-Co-S microspheres grown on reduced
graphene oxide/nickel foam for asymmetric supercapacitors [J]. Journal of Materials Research,
2019, 34(14): 2445-2455.
[3].Uwamahoro Evariste, Guohua Jiang, Bo Yu, Yongkun Liu, Zheng Huang, Qiuling Lu,
Pianpian Ma. One-step electrodeposition of molybdenum nickel-cobalt sulfide on Ni foam for
asymmetric supercapacitor. (under review).
[4].Yongkun Liu, Qiuling Lu, Zheng Huang, Shiqing Sun, Bo Yu, Uwamahoro Evariste, Guohua
Jiang, Juming Yao. Electrodeposition of Ni-Co-S nanosheet arrays on N-doped porous carbon
nanofibers for flexible asymmetric supercapacitors [J]. Journal of Alloys and Compounds,
2018, 762: 301-311.
[5].Bo Yu, Guohua Jiang, Wangcong Xu, Cong Cao, Yongkun Liu, Na Lei, Uwamahoro
Evariste, Pianpian Ma. Construction of NiMoO4/CoMoO4 nanorod arrays wrapped by Ni-Co-
S nanosheets on carbon cloth as a high-performance electrode for supercapacitor [J]. Journal
of Alloys and Compounds, 2019, 799, 415-424.
Synthesis and fabrication of electrodes based-carbon nanomaterials for energy
storage applications.

Graphical abstract
 1. Introduction to energy storage devices

Due to climate change and the fast development of the global economy, energy has become a
primary focus in the scientific and industrial communities. With concerns about environmental
pollution, increasing mining costs and the depletion of fossil fuel, there is an urgent need for an
efficient, clean and renewable energy source, and energy storage technique[1].
Although great efforts have been made on the development of high-performance Li-ion
batteries and fuel cells, the poor power capability and high maintenance cost have kept them away
from many applications. Recently, supercapacitors have drawn great attention because of their
high charge-discharge rate, long life cycle, outstanding power density and no short circuit concern
that are of concern with current batteries or fuel cells[2]. Supercapacitors, also known as ultra-
capacitors or electrochemical capacitors, store energy with an electric double layer (EDL)
capacitance achieved by ion adsorption or pseudo-capacitance dominated by a surface redox
reaction.
Pseudo-capacitors with conducting polymers or metal oxides as an electrode material,
although demonstrating high capacitive performance, but cannot maintain this performance after
prolonged cycling. On the other hand, EDL capacitors can be charged and discharged as many as
one million cycles without performance degradation. Furthermore, ion transportation is faster than
a redox reaction, resulting in a high charge-discharge rate and power density in EDL capacitors.
Currently, the energy density of EDL capacitors is generally 3-5 Wh/kg, which is one order of
magnitude below commercialized lithium-ion batteries (100-275 Wh/kg)[3]. Thus, increasing the
energy capacity with minimum sacrifice of power density is now a major topic in supercapacitor
research.
Currently, the three major commercialized energy storage devices are capacitors, batteries and
fuel cells. To illustrate the advantage of supercapacitors, the structure, mechanism and
performance comparison of those devices are discussed in the following sections.

1.1 Capacitors
A capacitor, which is a passive electrical device, stores energy as a charge in the electrical field
between two conducting plates called electrodes. Capacitors generally can release the stored
charge quite fast resulting in high power, but cannot store much energy. Conventional capacitors,
also known as electrostatic capacitors, consist of two conducting electrodes separated by an
insulating layer called a dielectric as indicated by Fig. 1.1. When applying an external voltage,
charges accumulated on the surfaces of the two electrodes which are isolated by an insulating
dielectric layer, thus, generating an electric field. The resulting electric field allows the device to
store energy.
Generally, a fuel cell consists of a cathode, an anode and an electrolyte in its construction.
The major difference among various types of fuel cells is the electrolyte. Common electrolytes in
both research and commercial devices are the aqueous alkaline solution, polymer membrane, and
ceramic oxide. The most popular fuel cell design is the hydrogen proton exchange membrane
(PEM) fuel cell. With hydrogen introduced to the anode, a catalyst oxidizes hydrogen turning
them into protons (hydrogen ions) and electrons. The PEM is designed to allow positively charged
ions to pass through to the other side, thus electrons accumulate on the anode side

Fig. 1.1 Schematic of an electrostatic capacitor[4].

1.2 Batteries
So far, batteries have become the most common power source for various applications in
industrial and consumer electronics. A battery is a device that converts chemical energy into
electrical energy through a redox reaction. A typical battery contains one or more electrochemical
cells.
Each electrochemical cell consists of two electrodes which are electrically connected by a
conductive electrolyte with anions (negative charge ions) and cations (positive charge ions). The
polarity of a cell is identified by the transport of the anions and cations. In the charging process,
the electrode with anions transport is called the anode or negative electrode, while the other
electrode with cations transport is called the cathode or positive electrode. Generally, batteries are
powered by a redox reaction with a reduction of cations at the cathode and oxidation of anions at
the anode as seen in Fig. 1.2. Currently, lithium-ion batteries represent the best electrochemical
cells with a high energy density of 120-170 Wh/kg.

Fig. 1.2 Schematic of a working lithium-ion cell[5].

1.3 Fuel cells

Similar to batteries, fuel cells convert the chemical energy of a fuel into electric energy. However,
fuel cells require no recharging and the byproduct of the reaction generally is environmentally
friendly like water and heat as shown in Fig.1.3. As long as the fuel supply is adequate and
consistent, the cell can work ideally without replacement with outstanding reliability.
Compared with thermomechanical methods, fuel cells do not have combustion as an
intermediate step, which results in a higher energy conversion efficiency of 40%-60%. For these
reasons, fuel cell technology has become a clean, economical and reliable solution for power
sources. Among all the commercialized energy storage alternatives, fuel cells hold one of the
highest energy densities above 500 Wh kg-1.
 Fig. 1.3 Schematic of a fuel cell[6].

1.4 Supercapacitors
Because of the slow power delivery of batteries and fuel cells and the urgent need for high power
energy storage systems, more and more attention has been given to supercapacitors.
Supercapacitors or electrochemical capacitors are regarded as potential alternative
candidates for energy storage devices including mobile phones, computers, electric automobiles,
military devices, portable media players, and home electronic products due to their higher power
output, faster charge-discharge characteristics, longer lifespan and safer operation[7-8].
The supercapacitors are usually divided into two types: electrical double layers (EDLs)
capacitor which accumulates the charges at the electrode/electrolyte interface and pseudo-
capacitor which is storing charges due to redox reaction. Pseudo-capacitors materials mainly
consist of conductive polymers and metal oxides, while EDLs consist of carbonaceous materials
such as activated carbon, carbon aerogel, carbon nanotube (CNT), carbon nanofibers (CNF), and
graphene[9]. The fast and reversible faradaic redox reactions of pseudo-capacitors materials can
help them to offer much higher specific capacitance and energy density than EDLCs while EDLCs
can offer a high power density. However, it is still tricky for supercapacitors to achieve a high
energy and power density needed, which limits its commercialized promotion.
The combination of these two energy storage mechanisms within hybrid materials has been
under deep investigation to fulfill the requirements posed by various applications [10]. The sizeable
potential window is the key to obtain high energy density for supercapacitors. Currently, the
strategy of assembling asymmetric supercapacitor (ASCs) device by coupling different anodes
and cathodes with separate potential windows is used to extend the potential operating window.
Thus to overcome this challenge, the high performance positive and negative electrodes are
needed.

Fig. 1.4 Assembled asymmetric supercapacitor.

1.5 Comparison of energy storage devices

The Ragone chart (Fig. 1.5) is a standard method to compare the energy storage performance
of various devices. The dash lines indicate the time required to charge or discharge the device.
From Fig. 1.5, we can see that compared with batteries or fuel cells, conventional capacitors have
very high power density, but relatively low energy density. It means that a conventional capacitor
can be charged or discharged very quickly and generate high power, but it cannot storage much
energy in unit mass or volume. On the other hand, batteries and fuel cells can store more energy
but have a poor dynamic performance.
Supercapacitors store more power than a battery and more energy than a capacitor. It means
that supercapacitors can be charged or discharged very fast and maintain reasonable energy stored
per unit mass. For this reason, it brings significant benefits in peak-power delivery applications,
like regenerative braking, electric vehicle acceleration, and uninterruptible power supply.
Besides bridging the power gap between capacitors and batteries, supercapacitors also hold
many other desirable properties that make them a promising candidate for the next-generation
energy storage device. The charge storing mechanism is a physical process without any chemical
or phase change, so that it is highly reversible and can be repeated for a large number of charge-
discharge cycles, more than 100,000 times. Also, they can be operated over a wide temperature
range.
 Fig. 1.5 Ragone plot for various energy storage devices[11].
2. Problem statement
Supercapacitors are still suffering from insufficient energy densities compared to the batteries
which affect their commercial development. A major challenge for current research is to improve
their energy densities without compromising their fundamental advantages.
3. Objectives
The objective of this research is to develop advanced electrodes for energy storage materials,
investigate and characterize and optimize their performance through the following engineering
aspects:
 Development of carbon-based composite electrode materials by low cost and
environmentally friendly methodology.
 Development of advanced anionic additives, which prevent the anodic dissolution of the
substrate and promote electron transfer during the preparation of the electrodes.
 Development of advanced dispersing agents for electrodeposition of carbon-based
materials.
 Fabrication of composite materials, investigation of microstructure, adhesion, composition
and electrochemical performance for application in electrodes of energy storage devices.
 4. Motivation
The future of the energy storage devices market is likely to witness the emergence of
electrochemical supercapacitors that will power the future of modern wearables and consumer
electronic products. Solar supercapacitors are also a thing from the future, which is expected to
have huge sales potentials in the wearable sensors landscape, especially in wearable health devices.
The ongoing research activities and developments in the power electronics industry continue
to hint at energy storage devices such as supercapacitors and batteries. With increasing
applications of energy storage devices in various industrial sectors, such as electronics, energy &
power, military & defense, and aerospace, the global market for energy storage devices is expected
to surpass U$ 5.5 billion by 2028. The exponential growth rate of the energy storage devices
market is expected to amplify lucrative opportunities for researchers, manufacturers, and other
stakeholders in the landscape.
5. Organization of research.
The research project is structured like the following.
In the first year: Each component of carbon-based materials will be studied to illustrate their
necessity, advantages and possible improvements. The components of energy storage devices such
as electrode materials, electrolytes and separators will be studied and prepared + course work.
In the second year: The material synthesis details and characterization results will be provided.
The characterization involves multiple techniques like scanning electron microscopy (SEM),
transmission electron microscopy (TEM), nitrogen isothermal adsorption, X-ray diffraction
(XRD), Fourier transform infrared spectroscopy (FTIR), X-ray photoelectron spectroscopy (XPS)
and Raman spectroscopy. Electrochemical measurements will be used to evaluate the
electrochemical performances of electrode materials and devices by extracting the specific
capacitance, energy density, and power density.
In the third year: Preparation of manuscripts and publications.
In the fourth year: Writing thesis and defense.
 6. Expected results and conclusion

By preparing the flexible electrode materials such as graphene oxide films and carbon cloth-based
electrodes will help to obtain the flexibles energy storage devices like supercapacitors which is
important in wearable electronic materials.

7. Research ethics

The experimental procedures will be considered following the ethical regulations on the care and
use of Laboratory of the University and will be approved by the school committee for laboratory
experiments.

8. Dissemination of outputs

To achieve the objectives, time action and effective targeting are needed to start up a new approach
for designing next-generation energy storage devices. Workshops, seminars, conferences, and
peer-reviewed international journals, as well as publishing manuals posters, will be exploited as a
means to achieve the desired goals.
 References
[1]. Hu N, Huang L, Gong W, et al. High-performance asymmetric supercapacitor Based on
hierarchical NiMn2O4@CoS core-shell microspheres and stereotaxically constricted graphene
[J]. ACS Sustainable Chemistry & Engineering, 2018, 6(12): 16933-16940.
[2]. Meng Y, Sun P, He W, et al. Construction of hierarchical Co-Ni-S nanosheets as a free-
standing electrode for superior-performance asymmetric supercapacitors [J]. Applied Surface
Science, 2019, 470: 792-799.
[3]. Fan L Q, Pan F, Tu Q M, et al. Synthesis of CuCo2S4 nanosheet arrays on Ni foam as binder-
free electrode for asymmetric supercapacitor [J]. International Journal of Hydrogen Energy,
2018, 43(52): 23372-23381.
[4]. Liu S, Jun S C. Hierarchical manganese cobalt sulfide core-shell nanostructures for high-
performance asymmetric supercapacitors [J]. Journal of Power Sources, 2017, 342: 629-637.
[5]. Goodenough JB, Park K S. The Li-ion rechargeable battery: a perspective[J]. Journal of the
American Chemical Society, 2013, 135(4): 1167-1176.
[6]. Choudhury A, Chandra H, Arora A. Application of solid oxide fuel cell technology for power
generation-A review[J]. Renewable and Sustainable Energy Reviews, 2013, 20: 430-442.
[7]. Bubna P, Advani SG, Prasad A K. Integration of batteries with ultracapacitors for a fuel cell
hybrid transit bus[J]. Journal of Power Sources, 2012, 199: 360-366.
[8]. Guo M, Gao H, Huang W, et al. Microwave-assisted rapid synthesis of NiCo2S4 nanotube
arrays on Ni foam for high-cycling-stability supercapacitors [J]. Journal of Alloys and
Compounds, 2019, 780: 164-169.
[9]. Lei X, Ge S, Tan Y, et al. Bimetallic phosphosulfide Zn-Ni-P-S nanosheets as binder-free
electrodes for aqueous asymmetric supercapacitors with the impressive performance [J].
Journal of Materials Chemistry A, 2019, 7(43): 24908-24918.
[10]. Huang Y, Zhao Y, Bao J, et al. Lawn-like FeCo2S4 hollow nanoneedle arrays on flexible
carbon nanofiber film as binder-free electrodes for high-performance asymmetric
pseudocapacitors [J]. Journal of Alloys and Compounds, 2019, 772: 337-347.
[11]. Jia H, Song Y, Wu J, et al. A novel P-doped MnCo2S4 nanoneedles assembled dandelion-
like structure for high performance hybrid supercapacitors [J]. Materials Letters, 2018, 233:
55-58.